We have investigated the electrostatic potential distribution in compact and nanoporous TiO2 films, deposited on conducting F-doped SnO2 substrate (FTO), which are used in dye-sensitized solar cells. The TiO2 films were immersed into aqueous electrolyte and excited from the FTO side by light pulses of a N-2 laser while the current response was measured as a function of time. The measurements were carried out as a function of the pH value of the electrolyte and at different electrostatic potentials. For compact TiO2 films, the sign of the transient current at short response times changed when the applied electrostatic potential or the pH value was decreased. This was not observed for mesoporous TiO2 films directly deposited onto the FTO substrate without a compact TiO2 layer. We interpret the results in terms of a macroscopic electric field across the compact layer which is changed by the applied potential or the pH of the electrolyte. In contrast, measurements on mesoporous TiO2 films indicate that the contact region is mainly field-free, and we explain our results by a very sharp electrostatic potential drop within the first layer of particles at the TiO2/FTO interface.